Cellulosic copolymer filter material



United States Patent O 3,366,582 'CELLULOSIC COPOLYMER FILTER MATERIAL James W. Adams, Schofield, and Henry W. Hoftiezer, Rothschild, Wis., assignors to American Can Company, New York, N.Y., a corporation of New Jersey @riginal appiication Apr. 28, 1964, Ser. No. 363,242, now Patent No. 3,256,372, dated June 14, 1966. Divided and this application Feb. 18, 1966, Ser. No. 537,598 3 Claims. (Ci. 260-2.5)

This invention is a division of our copending application Ser. No. 363,242, filed Apr. 28, 1964, now Patent No. 3,256,372. The invention relates to porous cellulosic products. These novel materials are produced from cellulosic pastes containing significant amounts of additives which produce novel properties in products produced therefrom. In one specific embodiment the invention relates to cigarette filters and in another embodiment the invention relates to materials having very high capacity to absorb and retain Water.

In accordance with the present invention it has been discovered that cellulosic fibers, when modified by the deposition or formation therein of polymers containing hydrophilic functional groups, can be formed into a light cohesive material suitable for filtering gases and absorbing liquids. This material is of particular utility in removing tars and other impurities from cigarette smoke.

Various methods of in situ polymerization of monomers within fibers such as cellulose have been taught in the prior art. Among these are deposition of monomer from the vapor phase; replacement of water, used to swell the fibers, with acetone, followed by treatment with an acetone solution of monomer and catalyst; and the anchored catalyst technique rst disclosed by Lipson et al., Nature, 157:590 (1946) and Landells et al., l. Soc. Dyers and Colonrists 671338-344 (1951). Any of these methods will produce suitable starting materials for the practice of my invention. It is preferred, due to economic considerations, to use the anchored catalyst technique.

It has been discovered that a certain class of in situ deposited polymers cause the resulting modified host ce1- luosic material to exhibit dispersing or lubricating properties when used alone or when mixed with unmodified cellulosic fibers. Because slurries of cellulosic materials such as cotton, rayon, wood pulp, or bast fibers are ordinarily coarse and clumpy, and lack fiow properties, these materials cannot be extruded without expending a large amount of power. The dispersed materials of the present invention are slippery to the touch, and may readily be eX- truded or otherwise formed into any desired shape. Previously, such dispersed fibers have been used in small amounts as strengthening additives for fabrics or papers. lf compositions containing the dispersed fibers were allowed to dry under ordinary conditions, for example, in air, or in a drying oven, the resulting products became more dense and hard as the percentage of dispersing fibers wasincreased. lf thick shaped objects were attempted to be formed, they tended to be board-like and have an irregular surface.

It has now been further discovered that these materials, when dried under certain conditions, will result in an unexpectedly different product. The product of this invention is a light, porous, cohesive, and generally white material possessing remarkable ability to filter impurities from gases and to absorb large amounts of liquids. This material in one embodiment is highly effective in filtering air or other gases, and when used as a cigarette filter, will achieve much greater removal of tars and other particulate matter from the smoke than conventionally used material of the same weight. This is true despite the fact that these new materials are lighter than conventional filter materials, are cohesive and homogenous, and permit Y alkali salts are defined to include the alkali 3,366,582 Patented Jan. 3f), 1968 smoke or other gases to be drawn therethrough very easily.

Alternative modes of carrying out our method are illustrated in FIGURE 1, which is in the form of a flow diagram.

The starting materials used in the practice of the invention are cellulosic fibers having deposited in situ therein a synthetic polymer of the general formula:

in which:

R is a hydrogen atom or a methyl group,

Y is OH, OM, or NH2,

M is an alkali metal or ammonium ion, and n is an integer greater than 500.

Various reactions producing the desired polymers will be immediately apparent to those skilled in the art. EX- amples of such methods are listed here, but this list is not intended to be exhaustive:

(1) Polymerize acrylonitrile in the fibers and hydrolyze with an alkaline solution to form alkali salts of polyacrylic acid.

(2) Polymerize methyl acrylate in the fibers and hydrolyze with an alkaline solution to form alkali salts of polyacrylic acid.

(3) Polymerize ethyl acrylate in the fibers and hydrolyze with an alkaline solution to form alkali `salts of polyacrylic acid.

(4) Polymerize acrylic acid or alkali salts of acrylic acid in the bers.

(5) Polymerize methacrylonitrile in the fibers and hydrolyze with acids to form polymethacrylic acid or hydrolyze with an alkaline solution to form alkali salts of polymethacrylic acid.

(6) Polymerize methacrylic acid or alkali salts of methacrylic acid in the fibers.

(7) Polymerize acrylamide in the fibers.

(8) Polymerize methacrylamide in the fibers.

(9) Form copolymers of any of the above monomers or copolymerize with a small amount of non-hydrolyzable monomers.

For purposes of the present specification and claims salts and ammonium salts.

The fibers produced by these procedures are slippery, gelatinous and highly swollen by the deposition therein of these hydrophilic polymers. These fibers, which are herein designated as hydrophilic polymer modified cellulosic fibers, are readily dispersed in water and aid in the dispersing of other, untreated cellulosic fibers. It is believed that a substantial portion of the polymer, estimated to range between 50 and 90 percent, is grafted ontoI the fibers and the remainder is occluded, for example, in the hollow core of the fibers. The mechanism by which the synthetic polymers are retained in the fibers is not critical, so long as they are bound thereto strongly enough that at least a substantial percentage is not leached out during the further processing of the fibers.

The products of the present invention may be formed from a blend of untreated fibers and fibers containing preferably from 20% to 80% by weight of polymer modified fibers. This embodiment is preferred for economic reasons because only a portion of the fibers need be processed in the polymer deposition step. However, if desired, all of the fibers used may contain polymer. In the latter case a lower polymer loading may be used, preferably in the range of from 20% to 40% by weight of polymer. Fibers of this type containing more than polymer have been produced and porous products made group metal therefrom possess properties very similar to those formed from fibers containing lower polymer loadings.

It is of central importance to the present invention that a method has been discovered by which cellulosic slurries can be produced which are at the same time both easily moldable and yet shape stable enough after molding to retain their form as integral Wet products. These slurries when extruded have the appearance of wet rope. The materials of the present invention, in other words, have properties of cohesion and liuidity analogous to those of a stiff grease.

These polymer-containing fibers are formed into a slurry of paste-like consistency, which contains from about 75% to 97% water. The amount of Water necessary to produce a paste-like consistency depends on the amount of polymer present in the fibers and on the length of the fibers. For example, a large amount of polymer in the fibers and/ or water is necessary to produce an extrudable paste from longer fibers such as those in softwood kraft pulp as compared with shorter fibers such as those in hardwood sulphite pulp, and even more is necessary in the case of still longer fibers such as jute or bast fibers. The optimum percentages of dispersing fibers and water for any particular length fibers which will result in a composition which is moldable yet shape stable after molding can be determined by one with ordinary skill in the art by routine experimentation. In contrast with slurries containing only unreacted cellulosic fibers, which are coarse to the touch, and ordinarily regarded as non-extrudable, since if extrusion through an orifice Iis attempted, the fibers will be dewatered and the aqueous portion expressed through the orifice, the pastes used in the present method are slippery to the touch, and can readily be expressed through an extrusion die to form a coherent rod. It is believed that these pastes are extrudable because the hydrophilic polymers present -in the polymer modied fibers impart a dispersing and lubricating character thereto with the unique distinction that the dispersing or lubricating medium is itself of a fibrous nature and therefore will no become segregated from any untreated fibers present during molding or shaping operations.

A suitable paste-like slurry can then be molded by extrusion, injection molding, or other pressure deformation into any desired configuration. In the case of cigarette filters, the slurry preferably is extruded into a cohesive cylindrical rod of the desired diameter. Gas filters having special configurations can be formed by extruding rods having different cross sections. If a particular desired configuration is not obtainable by extrusion, other moldingl techniques such as pressure molding, injection molding, etc., can be used, as will readily be apparent to those skilled in the art. A further advantage in the use of a fibrous dispersing agent is that much greater porosity can be achieved than could be through the use of a conventional non-fibrous dispersing agent, since the latter would have a tendency to occupy and clog the pores whereas the fibrous agents of the present invention which themselves consist of fibers having a hydrophilic polymer attached on and within the fibers become a part of the fibrous product and maintain the pore structure thereof.

In carrying out the method of the present invention it is important that the wet molded objects formed from the pastes or slurries described above are dried under suitable conditions whereby the pore structure is maintained. If these wet objects are permitted to dry in air or in an oven at atmospheric pressures, the pore structure will collapse and the resultant product will be dense and nonuniform.

The preferred method of drying to produce a product having the desired characteristics is freeze drying, as freezing is the best way to rigidify the internal structure of the shaped object. If the aqueous medium is removed while the article is frozen, shrinkage during drying is minimized, and the dry resultant product retains substantially the same size and internal structure as did the fibrous phase of the wet object. Conventional procedures may be followed in removing the aqueous medium, for example, subjecting the frozen objects to reduced pressure or radiant heat, or preferably simultaneously to both. Freeze drying results in a product having greater whiteness and uniformity than the other methods which might be substituted therefor, for example, solvent drying. The rate of drying is not critical, and does not appear to affect the properties of the final product. However, it is preferred to cause the ice present in the frozen objects to sublime as rapidly as possible without melting. The reduced pressure in the drying chamber permits the application of considerable heat, usually from a radiant heater, without melting the aqueous medium or damaging the objects. In a typical freeze drying operation, the chamber is evacuated to a pressure of about 2O microns of mercury and radiant heat is applied at about 250 F. As heat is applied, the pressure rises and later falls in the chamber as water vapor sublimes from the frozen objects.

While solvent drying has not been found to result in a product having all of the attributes of those produced by freeze drying, it is considered to be an equivalent, less costly method for producing porous articles such as filters where the requirements for whiteness and uniformity of structure are less stringent. ln carrying out the solvent drying procedure, the shaped object is treated with an organic solvent, usually by immersion therein. The organic solvent used should be of a relatively volatile nature so that removal thereof from the fibers may be effected without undue difiiculty. Examples of solvents which may be used are methanol, ethanol, propanol, acetone, and dioxane; further examples will be readily apparent to those skilled in the art. These organic solvents prevent hydrogen bonding, which occurs in an aqueous slurry, and thereby permit the drying of the wet objects into highly porous products. These solvents cause a swelling of the molded objects, which again contract on evaporation of the solvent to approximately the molded size.

Both of the above described drying procedures have in common the steps of effectively separating the individual fibers preparatory to drying followed by the removal of the liquid constituents of the molded articles while the fibers are so separated, with the result that the dry final product is highly porous. The porous product can easily be cut to further modify the shape thereof, if required.

The process of the present invention is particularly adaptable to the manufacture of cigarette lters. A paste of extrudable consistency can easily be extruded through an orifice having a diameter only slightly larger than that of a cigarette to form a cohesive continuous rod of the desired size. Shrinkage of the rods during drying is generally less than 5%, the product thus being not substantially smaller in diameter than the extruded column. Alternatively the filters, which are easily compressible, may be made slightly oversized and compressed when wrapped to assure a good fit in the wrapper. If the extrusion die is chilled, the freezing step can be initiated during the extrusion step. If the extruded column is passed directly into a chilling medium such as liquid nitrogen, the freezing is nearly instantaneous, and distortion of the rods in further processing minimized. The rod may be dried continuously and cut into suitable lengths for filters when dry, or may be cut into such lengths prior to drying. Also suitable is a batch process wherein the extruded column is first cut into rods of suitable length to fit into a drying chamber, and after drying the rods are further cut into shorter sections suitable for cigarette filters. Such filters can also be produced by forming the slurry into a sheet, and cutting cylindrical plugs from said sheet before or after drying.

The present method is also readily adaptable to the formation of cigarette filters containing special absorptive ingredients to assist in the selective removal of harmful impurities in tobacco smoke. For example, activated charcoal may be added to the paste prior to extrusion to act as a filtering aid. Other filter assisting additives will suggest themselves to those skilled in the art.

An important advantage of the freeze drying method of the present invention is the ability to control the resistance of the final product to the flow of air therethrough with a high degree of accuracy. With any given polymer, this characteristic can be controlled by several process variables, including the freezing rate, the fiber size, and the percentage of solids in the slurry. As the freezing rate is increased, the pores become finer and more numerous, making it more difficult to draw air through the product. However the density remains the same since the amount of water removed is the same. To illustrate this phenomenon, cylindrical filters based on wood pulp were produced, holding all other process variable constant while varying the rate of freezing. Filters frozen at F. caused a pressure drop of 1.5 inches of water in a stream of air passing therethrough at a rate of 1000 cubic centimeters per minute whereas filters having the same density but frozen more quickly at 10 F. caused a pressure drop of 4.0 inches of Water in a stream of air passing there-through at the same rate. As smaller fiber sizes are used, the resistance to air flow through the product produced becomes greater. Also, as the fiber content of the slurry is increased, the density and air resistance of the product are increased. For producing cigarette filters, a solids content in the slurry of about 10% is preferred, but satisfactory results can be achieved if this percentage is as low as 3%. However, solids contents in the vicinity of 10% are preferable for economic reasons because less 4water need be removed in the subsequent drying steps. The final dry porous materials of this invention generally have a bulk specific gravity ranging between 0.04 and 1.15 grams per cubic centimeter, and any value within this range can easily be produced by properly selecting the values for the process variables as discussed hereinabove.

The porous articles of the present invention have a high capacity to absorb and retain Water or other aqueous media, and therefor are useful for such purposes as dental pads, sanitary napkins, and absorbent pads incorporated in fresh lmeat packages. While the dried poro-us products are good water absorbers, it has been discovered that further marked increases in this characteristic can be obtained by compressing the porous dried product. The compressed material appears to possess significant elastic memory when wetted, and therefore balloons out when contacted by water.,As shown in Table II infra, this cornpressed material absorbs significantly more water on a volume basis than the absorbent component of commercially available tampons. It is apparent from these data that the materials of the present invention are unexpectedly good Water absorbing agents. A readily 0bservable and distinct difference between the commercially available tampon material andthe modified cellulosic materials of the present invention is that the latter retain mosture much better, with noticeably less dripping.

The following examples further illustrate the present invention, which is not limited thereto.

Example 1 Two hundred grams of bleached Canadian softwood kraft pulp were added to a vessel containing 73 grams of ferrous sulphate heptahydrate dissolved in liters of water. The slurry was mixed for l5 minutes and damp dried in a hand operated press to 39 percent fiber solids. The damp fibers were then dried at 105 C. for 16 hours. The dry fibers were then reslurried in a steam jacketed ribbon blendor reactor equipped with a reflux condenser with 2O liters of distilled water, continuously mixed, heated to 90 C. in a nitrogen atmosphere, and cooled to 60 C. before adding one liter of inhibitor-free acrylontrile. One hundred milliliters of 6 percent H2O2 solution were added as the mixing continued, and the mixture was refluxed moderately for one hour. Three hundred twenty grams of fibers containing 37.5 percent polyacrylonitrile were produced. Two hundred fifty grams of these fibers were added to 4.7 liters of water containing 50 grams of dissolved NaOH and reacted for 2 hours at 90C. in order to hydrolyze polymerized acrylonitrile to sodium polyacrylate. The resulting paste containing hydrophilic polymer-modified cellulosic fibers was diluted to 2.5 percent solids, neutralized to pH6 with H2SO4, concentrated to 10 percent solids by screening, and extruded through an 8.34 mm. inside diameter die. The f extrudate was cut into l2 centimeters lengths, frozen at -25 C. and dried, While frozen, in a partial vacuum while exposed to radiant heat for approximately 6 hours in a conventional freeze dryer the heater of which was set at 250 F. The product consisted of tan colored self sustaining, porous rods 8 millimeters in diameter having a density of 0.11 grams per cubic centimeter.

Example 2 White cigarette filters were produced by eliminating the step of drying the iron-containing fibers, thereby preventing discoloration due to oxidation of a portion of the iron. The blendor reactor of Example l was used to slurry 1.5 kilograms of bleached Canadian softwood kraft wood pulp in 15 liters distilled water containing 1.8 grams of dissolved ferrous ammonium sulphate hexahydrate. The pH of the slurry was adjusted to 3.5 by adding lO percent H2804. The slurry was heated to 90 C. under nitrogen, cooled to 60 C. before adding 1.9 liters of inhibitor-free acrylonitrile and 37 milliliters of 10 percent H2O2. The mixture was reacted for one hour at v 90 C. to Vproduce 2.45 kilograms of fibers containing 39 percent polyacrylonitrile. One kilogram of this polymermodified wood pulp was added to 18.8 liters of water containing 200 grams of dissolved NaOH, and reacted at 90 C. for 2 hours. One hundred and fifty grams of the resulting 5 percent solids content paste comprising hydrophilic polymer-modified fibers, were blended with 7.5 grams of bleached Western softwood kraft woodpulp in 600 milliliters of water and enough H2804 -to adjust the pH to 8.0. The resulting slurry contained 50 percent treated and 50 percent untreated fibers. This slurry was screened to 10 percent solids, extruded and freeze dried as in Example 1 to produce white porous rods having a density of 0.12 grams per cubic centimeter.

Example 3 The process of Example 2 was followed in the reaction of 1.5 kilograms of bleached western softwood kraft wood pulp with 3.75 liters of inhibitor free acrylonitrile. The wood pulp was slurried in 20 liters of water and polymerization was initiated by treating the slurried pulp with 1.8 grams of dissolved ferrous ammonium sulfate hexahydrate, adjusting the pH to 3.9 with 10 percent sulfuric acid and adding the prescribed amount of acrylonitrile simultaneously with 38 milliliters of 10 percent hydrogen peroxide. Fibers containing 58 percent polymerized acrylonitrile were produced by reiluxing this mixture for 1 hour. One kilogram of the polymer modified wood pulp was added to 18 liters of water containing 1 kilogram of dissolved sodium hydroxide. While mixing r this slurry in the ribbon blendor reactor it was heated to 90 C. and held there for one hour. Six hundred grams of paste containing hydrophilic polymer modified were frozen and freeze dried to produce white, lporous rods that had a density of 0.15 gram per cubic centimeter.

Example 4 The process of Example 2 was followed to react 20 5 pounds of bleached Canadian softwood kraft wood pulp with 58 pounds of inhibitor-free acrylonitrile. The wood pulp was slurried in 75 gallons of water and polymerization was initiated by treating the slurried pulp at pH 3.9 with 23 grams of dissolved ferrous ammonium sulfate hexahydrate, followed by the addition of the prescribed amount of acrylonitrile and 460 milliliters of 10 percent 8 Example 5 TABLE IL WATER ABSORBENCY OF CELLULOSIC MATERIALS Properties of Dry illaterial Water Absorption Material Weight, Volume, Density, Amount at ML/g. Dry Ml./ec. grams ce. g./ee. Saturation, Material Dry ml. Material Tampon 1 1. 6 3. 5 0. 46 24. 4 15 7.0

Blotter Paper i 2. 4 4. 7 0. 51 7 1. 9 1. 5 Pressed, Freeze Dried Material of Example IV 0. 33 0. 45 0. 73 5. 0 15. 2 11. 1

hydrogen peroxide. Fibers containing 67 percent polym- Example 6 erized acrylonitrile were yproduced by reuxing this mixture for one hour. One kilogram of the polymer-modified wood pulp was added to 18 liters of water containing one kilogram of dissolved sodium hydroxide. While mixing this slurry in a 28-liter ribbon blendor it was heated to 90 C. and held there for one hour. Six hundred grams of paste containing hydrophilic polymer-modified iibers formed in this reaction were mixed for 3 minutes with 30 grams of bleached aspen sulfite pulp and 2 liters of water. The slurry pH was adjusted to 6.0 by adding 10 percent sulfuric acid before filtering the fibrous mixture on a drum filter. The wet mat containing 9 percent solids was extruded through an S34-millimeter diameter, round die. Twelve centimeter sections of the extruded wet rope were frozen and freeze dried to produce white, porous rods that had a density of 0.10 gram per cubic centimeter. Cigarettes were prepared for smoking tests by replacing the filters in commercially available cigarettes with weighed and measured sections of the freeze dried rods. The sizes and weights of filters in five other popular brands of cigarettes were also determined before smoking several samples to the same butt length. The moist filters Were then removed and weighed to determine amounts of water plus tars absorbed. The moist filters were air dried at room temperature for 16 hours and weighed again to measure tar content. Results of this study, summarized in Table I, show that the filters of this invention 5 absorbed 55 percent more tars than the most efficient commercial cigarette filter tested. The term tars as used herein is intended to include all particulate matter, non-volatile at room temperature, that is removed from the smoke.

The process of Example 2 was followed to prepare wood pulp fibers containing 66 percent polyacrylonitrile. One kilogram of the resulting polymer-modified wood pulp was added to 18 liters of water containing one kilogram of dissolved sodium hydroxide. This slurry was mixed and heated to 90 C. Land held there for one hour. One hundred eighty grams of the resulting paste of polymer-modified wood pulp fibers containing hydrolyzed :polyacrylonitrile was mixed with 6 grams of bleached Canadian softwood kraft wood pulp and 600 milliliters of water. The slurry pH was adjusted to 8.0 by adding 10 percent sulfuric acid before filtering the fibers on a handsheet mold screen. The wet mat containing solids. was extruded through a 7.5-millimeter inside diameter, 7-inch long section of copper tubing. Twelve centimetery sections of the extruded wet rope were immersed in methyl alcohol for 5 minutes where they swelled to a diameter to 11 millimeters. Porous dry rods, 8 millimeters in diameter, were made by placing the alcohol soaked ropes on blotting paper and drying them at 40 C. The rods had a density of 0.11 gram per cubic centimeter.

Example 7 60 monium sulfate hexahydrate in 100 milliliters of water,

TABLE I.-PERI"ORMANCE OF CIGARETTE FILTERS IN SMOKING TEST Filter Properties Weight of Weight of Water and Tars Filter Filter Composition Tars Absorbed, Absorbed, Length, Volum Weight, ing/cc. of rug/cc. of mm. ce. g. Filter Filter Cellulose Acetate 1.0 187 25 12 Crimped Paper 1. 25 218 33 16 TotalDFllter CeliuloseAcetate Plus Char- 16 0. 8 155 3l 1G coa lChercoal Portion 8 0. 4 089 24 17, 5 Cellulose Acetate... 20 1. 0 190 29 17 E o 17.5 .9 .155 33 19 Filter of Example 1V:

Blend of Wood Pulp und Sodium loly- 20 1.0 .112 52 Q9, 5

acrylato-Containing Wood Pulp.

1.8 liters of inhibitor free acrylonitrile and 37 milliliters of 10 percent hydrogen peroxide. The nitrogen gas ushing was stopped, and the treated pulp slurry was mixed in the sealed reactor while being lheated to 89 C. This condition was maintained for one hour to prepare 2.48 kilograms of fibers containing 39 percent polymerized acrylonitrile. Two hundred fifty grams of the polymer modified wood pulp was added to 4.7 liters of water containing 50 grams of dissolved sodium hydroxide. While mixing this slurry in the ribbon blendor reactor it was heated to 90 C. and held there for 2 hours to hydrolyze some of the polymerized acrylonitrile to sodium polyacrylate. Two and live-tenths kilograms of paste from this reaction was diluted to liters with water, treated with percent sulfuric acid to pH 6 and filtered on a 180- mesh screen. The wet mat containing polymer-modified fibers and having 14 percent solids was extruded through an S34-millimeter, inside diameter brass tube. Twelvecentimeter sections of extruded wet rope thus formed were chilled at 25 C. until frozen. The frozen rods were freeze dried and resulted in porous filter sections 8 millimeters in diameter, off-white in color, and with a density of 0.15 gram per cubic centimeters. A twentymillimeter long section of the porous material was substituted for the filter in a commercially available cigarette. Smoking tests established that the freeze dried, cotton linter filter had a tar absorbing efficiency of 30 milligrams per cubic centimeter of filter, as compared to 12-19 milli- -grams per cubic centimeter of filter in the commercially available cigarette tested.

Example 8 Five grams of bleached Canadian softwood kraft wood pulp were soaked in 100 mill-ilitens o-f 0.2 percent ferrous sulfate for 5 minutes at room temperature. The pulp was filtered from the ferrous sulfate solution, squeezed and dried at 105 C. for 30 minutes. The iron-treated pulp was slurried in a mixture of 50 grams of methacrylic acid and 50 miliiliter's of distilled water before adding 0.5 milliliter of 3-0 percent hydrogen peroxide. After mixing, the slurry was placed in a 15G-milliliter capacity glass jar, sealed tightly with a screw type cap and incubated for 18 hours at 38 C. The viscous reaction mixture was treated with 25 grams of 45 percent sodium hydroxide to adjust the pH to 6.0 before extruding the paste containing polymer-modied fibers through an S34-millimeter, inside diameter brass tube. Ten-centimeter sections of wet rope thereby obtained were chilled at 25 C. until thoroughly frozen and then freeze dried. The white, porous 'ltter sections produced by freeze drying the ropes had a density of 0.5 gram per cubic centimeter.

While particular embodiments of the invention have been described to give a clear understanding of the invention, modification thereto will be apparent to those skilled in the art. Therefore the invention is intended to be limited only as required by the prior art and the scope of the appended claims.

We claim:

1. A porous, shaped object comprising natural cellulose fibers, at least a portion of said fibers having chemically bonded therein and thereon by in situ formation a polymer selected from the group consisting of polyacrylamide, polymethacrylamide, alkali salts of polyacrylic acid, a'lkali salts of polymethaorylic acid, and copolymers thereof, said polymer being present in an amount between about 20 percent and 90 percent of the total weight of said object, said object having a dry density of betwen 0.04 and 1.15 grams per cubic centimeter.

2. 'Dhe product olf claim 1 wherein said object is in the shape of a slender, coherent rod having a density between about 0.04 and 0.5 gram per cubic centimeter.

3. The product of claim 1 wherein said object initially has a density of between 0.04 and 0.5 gram per cubic centimeter and is compressed in the dry state to a density between 0.5 and 1.15 grams per cubic centimeter.

No references cited.

WILLIAM H. SHORT, Primary Examiner.

I. NORRIS, Assistant Examiner. 

1. A POROUS, SHAPED OBJECT COMPRISIING NATURAL CELLULOSE FIBERS, AT LEAST A PORTION OF SAID FIBERS HAVING CHEMICALLY BONDED THEREIN AND THEREON BY IN SITU FORMATION A POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYACRYLAMIDE, POLYMETHACRYLAMIDE, ALKALI SALTS OF POLYACRYLIC ACID, ALKALI SALTS OF POLYMETHACRYLIC ACID, AND COPOLYMERS THEREOF, SAID POLYMERS BEING PRESENT IN AN AMOUNT BETWEEN ABOUT 20 PERCENT AND 90 PERCENT OF THE TOTAL WEIGHT OF SAID OBJECT, SAID OBJECT HAVING A DRY DENSITY OF BETWEEN 0.04 AND 1.15 GRAMS PER CUBIC CENTIMETER. 